Time-dependent 3-D modelling of laser surface heating for the hardening of metallic materials

A numerical code for the time-dependent three-dimensional modelling of the laser surface heating for the hardening of metallic materials has been developed by the authors. The temperature-dependence of the thermal properties of the material (stainless steel) is taken into account in the frame of a heating process that doesnt lead to material melting or evaporation. Calculations have been carried out for various dimensions of the parallelepiped-shaped and of the square-shaped spot of the laser beam, as well as for different scanning velocity and for different levels of the laser source power. Various patterns of the laser spot path have also been studied, including a single-pass hardening pattern, a double-pass hardening pattern with and without overlapping, multiple discontinuous and continuous hardening patterns and spiral hardening patterns. The presented results show how the proposed model can be usefully employed in the prediction of the time-evolution of temperature distribution which arises in the workpiece as a consequence of the laser-workpiece interaction under operating conditions typically encountered in industrial applications of the laser hardening process.Received: 29 July 2003, Published online: 30 September 2003PACS: 42.62.Cf Industrial applications - 44.05. + e Analytical and numerical techniques     

Comparison of different techniques for the FLUENT$^{\copyright}$-based treatment of the electromagnetic field in inductively coupled plasma torches

A new technique for using the CFD commercial code FLUENT ^©^{\copyright} to simulate inductively coupled plasma torches by means of two-dimensional axisymmetric models is presented. The method is based on an external user-defined function (UDF) which fully solves the electromagnetic field equations, letting the FLUENT ^©^{\copyright} built-in module calculate only the plasma temperature and velocity fields inside the torch region. In this framework, computations have been carried out for LTE, optica lly thin argon plasmas at atmospheric pressure, using extended grid models with either magnetic dipole or vanishing vector potential boundary conditions for the electromagnetic field. It is shown that our newly developed technique is up to 60% faster on each iteration than that using user-defined scalars (UDS) previously proposed in the literature, as the need of solving flow field equations also outside the plasma zone is eliminated. Calculations are also performed using exact integral boundary conditions for the vector potential, as given by the standard electromagnetic field approach, taking into account the effects of both exciting and induced currents. The corresponding results are compared with the approximate ones obtained by employing extended grid models, showing that for small radial dimensions of the electromagnetic field domain, the magnetic dipole boundary conditions give more realistic solutions than those assuming a vanish ing vector potential.     

Polymer adsorption onto random planar surfaces: interplay of polymer and surface correlations

We study the adsorption of homogeneous or heterogeneous polymers onto heterogeneous planar surfaces with exponentially decaying site-site correlations, using a variational reference system approach. As a main result, we derive simple equations for the adsorption-desorption transition line. We show that it is preferable to have a small amount of strongly adsorbing sites or monomers rather than a greater amount of weakly adsorbing ones. The results are discussed with respect to their implications for the physics of molecular recognition.     

Dehnungsverhalten von Polyäthylen-Schmelzen

Zusammenfassung In einem Dehnungsrheometer werden Spannungs-Dehnungs-Diagramme von Polyäthylen-Schmelzen bei 150 °C und bei konstanter Dehnungsgeschwindigkeit gemessen ( zwischen 0,001 und 1 sec^–1). Weiterhin wird der reversible (elastische) Dehnungsanteil bestimmt. Messungen mit einem Dehnungstester für Kunststoff-Schmelzen ergänzen die Ausführungen.Die Ergebnisse zeigen deutlich, daß bei Dehnung mit zunehmender Verformungsgeschwindigkeit die Dehnungsviskosität nicht abnimmt, im Gegensatz zu dem bekannten strukturviskosen Verhalten bei Scherung.Bei Dehnungen bis zu=1 kann das Verhalten unabhängig von beschrieben werden, wenn als viskoelastische Materialfunktion die Dehnungs-Spannviskosität betrachtet wird. In diesem Bereich von gilt dabei die BeziehungT(t)=3 _s (t) mit _s (t) als zeitabhängige Scherviskosität im linear-viskoelastischen Bereich.Bei größeren Dehnungen und nicht zu kleinen Dehnungsgeschwindigkeiten zeigt verzweigtes Polyäthylen eine zusätzliche starke Spannungszunahme. In dem Bereich dieser zusätzlichen Verfestigung ist das Verhalten im wesentlichen eine Funktion der Dehnung und fast unabhängig von . Die zusätzliche Verfestigung scheint eine Folge der Verzweigungsstruktur des verzweigten Polyäthylens zu sein, da bei Linear-PE ein derartiger Verlauf des Spannungs-Dehnungs-Diagramms nicht beobachtet wird.Die Betrachtung des reversiblen Dehnungsanteils _R zeigt bei der ausführlich untersuchten Schmelze I (verzweigtes PE) drei verschiedene Bereiche: Unterhalb einer Grenzdehnungsgeschwindigkeit ist _R =0, unterhalb einer Versuchszeitt ^** ist _R =. Im dazwischenliegenden Bereich treten elastische und viskose Dehnungsanteile auf,= _R + _V , wobei für niedrige gilt, daß _R lg . Die Grenze wird der Frequenz der thermisch aktivierten Platzwechsel zugeordnet,t ^** erscheint als Zeit, innerhalb der die Verhakungen wie fixierte Vernetzungen wirken.In dem Anhang wird der Einfluß der Grenzflächenspannung zwischen PE-Schmelze und Silikonöl auf die Ergebnisse der Dehnungsversuche diskutiert.

---

Summary Stress-strain relations for different PE melts are measured at 150 °C in an extensional rheometer under the condition of a constant extensional strain rate ( between 0,001 and 1 sec^–1). Further, the recoverable (elastic) portion _R of the total strain ( in Hencky's measure) is determined and additional measurements with a tensile tester for polymer melts are described.The results show clearly that in extension there is no decrease of the tensile viscosity with increasing deformation rate, in contrast to the well-known pseudoplastic behaviour in shear. Within total strains<1 the tensile behaviour can be described independently from by means of a viscoelastic material function called stressing viscosity . In this range of the relation _T (t)=3 _s (t) holds, where _s (t) is the stressing viscosity in shear in the linear viscoelastic range. For larger tensile strains and not too small branched PB shows a remarkable increase in stress. This work-hardening behaviour is mainly a function of and almost independent from . This additional hardening seems to be due to the branches in branched PE, because linear PE does not show this effect.The discussion of the recoverable tensile strain _R gives three regions of tensile rate: Below a critical there is _R =0. At times shorter thant ^** the equation _R = is valid. Within these limits both elastic and viscous portions of the total strain= _R + _V exist. may correlate with the frequency of the thermally activated position changes of the molecular segments.t ^** is assumed to be the time for the entanglements to act as fixed cross-links.In the appendix the influence of the interface tension between PE melt and silicone oil on the results of the tensile experiments is discussed.

---

---

Vorgetragen auf der Deutschen Rheologen-Tagung, Berlin, 11.-13. Mai 1970.

---

An der Weiterentwicklung des Dehnungsrheometers, an der Durchführung und Auswertung der Messungen waren die HerrenB. Kienle, F. Landmesser, M, Reuther undF. Scherr beteiligt. Herr Dr.F.Ramsteiner und HerrH. Schroeck haben sich um die Herstellung der Stränge aus Linear-PE bemüht. Herr Dr.W. Ball besorgte die GPC-Messungen und Herr Dr.P. Simak die Ultrarot-Untersuchung. Den vorgenannten Herren sei für ihre Hilfe beim Zustandekommen dieser Arbeit gedankt. Herrn Dr.H. Baur danke ich für wertvolle Diskussionen.     

Stereoselective methadone disposition after administration of racemic methadone to anesthetized Shetland ponies assessed by capillary electrophoresis

The enantioselectivity of the pharmacokinetics of methadone was investigated in anesthetized Shetland ponies after a single intravenous (0.5 mg/kg methadone hydrochloride; n = 6) or constant rate infusion (0.25 mg/kg bolus followed by 0.25 mg/kg/h methadone hydrochloride; n = 3) administration of racemic methadone. Plasma concentrations of l -methadone and d -methadone and their major metabolites, l - and d -2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), respectively, were analyzed by CE with highly sulfated γ-cyclodextrin as chiral selector and electrokinetic analyte injection from liquid/liquid extracts prepared at alkaline pH. In both trials, the d -methadone concentrations were lower than those of l -methadone and the d -EDDP levels were lower than those of L-EDDP. For the case of a single intravenous bolus injection, the plasma concentration versus time profile of methadone enantiomers was analyzed with a two-compartment pharmacokinetic model. l -methadone showed a slower elimination rate constant, a lower body clearance, and a smaller steady-state volume of distribution than d -methadone. d -methadone and d -EDDP were eliminated faster than their respective l -enantiomers. This is the first study that outlines that the disposition of racemic methadone administered to anesthetized equines is enantioselective.     

Cross‐Reactive Sensor Arrays for the Detection of Peptides in Aqueous Solution by Fluorescence Spectroscopy

A simple but powerful method for the sensing of peptides in aqueous solution has been developed. The transition‐metal complexes [PdCl₂(en)], [{RhCl₂Cp*}₂], and [{RuCl₂(p‐cymene)}₂] were combined with six different fluorescent dyes to build a cross‐reactive sensor array. The fluorescence response of the individual sensor units was based on competitive complexation reactions between the peptide analytes and the fluorescent dyes. The collective response of the sensor array in a time‐resolved fashion was used as an input for multivariate analyses. A sensor array comprised of only six metal–dye combinations was able to differentiate ten different dipeptides in buffered aqueous solution at a concentration of 50 μM . Furthermore, the cross‐reactive sensor could be used to obtain information about the identity and the quantity of the pharmacologically interesting dipeptides carnosine and homocarnosine in a complex biological matrix, such as deproteinized human blood serum. The sensor array was also able to sense longer peptides, which was demonstrated by differentiating mixtures of the nonapeptide bradykinin and the decapeptide kallidin.     

催化剂和供氢剂对渣油模型化合物裂化反应选择性的影响

供氢剂与分散性催化剂协同作用对于传统的煤液化体系和渣油加氢裂化体系非常重要。通过活化分子氢及煤分子，使液化反应在较低的温度下进行以减少副反应，继而提高氢转移效率，增加液体产物产率。供氢剂和催化剂起促进煤分子裂化的作用。将供氢剂与催化剂的协同作用应用于渣油加     

Adamantane-Based Tripodal Thioether Ligands Functionalized with a Redox-Active Ferrocenyl Moiety for Self-Assembled Monolayers

Self-assembled monolayers (SAMs) can decorate surfaces with `smart′ functional units possessing reversible stimulus-response behavior for optical, thermal, magnetic or redox-chemical stimuli. An independent performance of individual functional groups in such a film is desirable, which can be, in particular, ensured by fairly large lateral separations between tailgroups in the SAM. Adsorbate molecules with multiple attachment points are very promising in this context owing to their large surface footprint, which covers a surface area exceeding the lateral dimensions of the functional groups. To address these design constraints, novel tridentate long-chain tripodal thioether ligands with central adamantine units and a redox-active ferrocenyl tailgroup, 1-[4-(ferrocenylethynyl)phenyl]-3,5,7-tri[(4-n-octylsulfanyl)phenyl]adamantine (T8) and 1-[4-(ferrocenylethynyl)phenyl]-3,5,7-tri[(4-n-dodecylsulfanyl)phenyl]adamantine (T12), were synthesized and used as tripodal adsorbate molecules for the fabrication of redox-active ferrocenyl-terminated SAMs on Au(111). These SAMs were characterized by X-ray photoelectron spectroscopy, near edge X-ray absorption fine structure spectroscopy and sum frequency generation spectroscopy. The data suggest that T8 and T12 form almost contamination-free, well-aligned and fairly densely-packed SAMs on Au(111) with laterally separated ferrocenyl units. The SAMs show a homogeneous binding chemistry, an important requirement for high fidelity SAMs. SFG results indicate lateral interactions between neighboring molecules via the long-chain binding units.     

OH-radical induced degradation of hydroxybenzoic- and hydroxycinnamic acids and formation of aromatic products—A gamma radiolysis study

The OH-radical induced degradation of hydroxybenzoic acids (HBA), hydroxycinnamic acids (HCiA) and methoxylated derivatives, as well as of chlorogenic acid and rosmarinic acid was studied by gamma radiolysis in aerated aqueous solutions. Primary aromatic products resulting from an OH-radical attachment to the ring (hydroxylation), to the position occupied by the methoxyl group (replacement –OCH₃ by ?OH) as well as to the propenoic acid side chain of the cinnamic acids (benzaldehyde formations) were analysed by HPLC–UV and LC–ESI–MS. A comparison of the extent of these processes is given for 3,4-dihydroxybenzoic acid, vanillic acid, isovanillic acid, syringic acid, cinnamic acid, 4-hydroxycinnamic acid, caffeic acid, ferulic acid, isoferulic acid, chlorogenic acid, and rosmarinic acid. For all cinnamic acids and derivatives benzaldehydes were significant oxidation products. With the release of caffeic acid from chlorogenic acid the cleavage of a phenolic glycoside could be demonstrated. Reaction mechanisms are discussed.